Process for the production of polyarenazole yarn

Cross-reference to related applications This application claims the benefits of US Application No. 60 / 665,885, which was filed dated March 28, 2005, the disclosure of which is incorporated herein by reference.

The present invention relates to a rigid rod-shaped polymer, a method for producing the polymer, and a filament and yarn containing the polymer.

Advances in polymer chemistry and technology over the past few decades have made it possible to produce high performance polymer fibers. For example, a liquid crystal polymer solution of a rigid rod-shaped heterocyclic polymer is spun to produce moist fibers, the solvent is removed to dry the fibers, and the dried fibers are heat treated. This makes it possible to generate high-strength fibers from the liquid crystal solution. Examples of high performance polymer fibers include poly (p-phenylene benzobisthiazole) (PBZT) and poly (p-phenylene-2,6-benzobisoxazole) (PBO).

Fiber strength is typically interrelated with one or more polymer parameters, including composition, molecular weight, intermolecular interactions, backbone, residual solvent or water, polymer orientation and process history. Is done. Fiber strength typically increases with, for example, the length (ie, molecular weight) of the polymer, the orientation of the polymer, and the presence of strong intermolecular interaction attractive forces. High molecular weight rigid rod polymers are useful for producing polymer solutions (dopes) that can be spun into fibers, and typically higher molecular weights result in higher fiber strength. It gets higher.

The molecular weight of rigid rod polymers is typically monitored and interrelated by making viscosity measurements of one or more dilute solutions. Therefore, the relative viscosity of the dilute solution (V is typically used for the purpose of monitoring the molecular weight of the polymer._relOr "η"_relOr "n_rel) And intrinsic viscosity V_inhOr "η"_inhOr "n_inh) Measured value is used. The formulas for the relative viscosity and intrinsic viscosity of the dilute polymer solution are V_inh= ln (V_rel) / C [In the equation, ln is the natural logarithm function, and C is the concentration of the polymer solution] It is related according to. V_relIs a unitless ratio, therefore V_inhIs expressed as a unit of inverse concentration, typically deciliters per gram (dl / g).

Patent Document 1 describes rigid rod-shaped polymer fibers having strong hydrogen bonds between polymer chains, such as polypyridobisimidazole. Examples of polypyridobisimidazole include poly (1,4- (2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d: 5,6-d'] bisimidazole, which Can be produced by causing condensation polymerization of 2,3,5,6-tetraaminopyridine and 2,5-dihydroxyterephthalic acid in polyphosphoric acid. One-dimensional or two-dimensional products such as fibers. It is described in Patent Document 1 that it is necessary to increase the molecular weight of polypyridobisimidazole when manufacturing films, tapes, etc., but such a molecular weight is 0.25 g of the polymer converted to methanesulfonic acid. Relative viscosity when added at a concentration of / dl and measured at 25 ° C ("V"_relOr "η"_rel) Corresponds to at least about 3.5, preferably at least about 5, and more particularly equal to or greater than about 10. Patent Document 1 also states that poly [pi] having a relative viscosity of about 12 or more. Lidobis imidazole-2,6-diyl (2,5-dihydroxy-p-phenylene)] gives very good fiber spinning results and has a relative viscosity of over 50 (intrinsic viscosity of about 15.6 dl / g or more). It is also disclosed that (corresponding to) can be achieved. Thus, to produce rigid rod-like polymers with even higher molecular weights, such as polypyridobis imidazole, which are characterized as having a higher viscosity in the polymer solution, and to produce fibers from the solution of such polymer. , Further technological progress is required.<patcit num="1"><text>Sikkema et al. US Pat. No. 5,674,969</text></patcit>

Abstract of the invention The present invention is, in part, directed to a method for the continuous production of polyarene azole multifilament yarn, which method is: a) A filament is formed by extruding a solution containing a polyarene azole polymer and polyphosphoric acid through a number of orifices. b) Generate multifilament yarn from the filament c) By heating the yarn to a temperature of about 120 ° C or higher within about 2 minutes, at least some of the polyphosphoric acid contained in the yarn is hydrolyzed. d) Rinse at least some of the polyphosphoric acid hydrolyzate from the yarn and e) Dry the washed yarn and f) In some cases, heat the yarn above about 300 ° C and g) Collect the yarns at a speed of at least about 50 meters per minute, Consists of that.

One suitable fiber production method relates to a method of passing the extruded filament through an air gap and then through a coagulation bath.

In certain embodiments, the method additionally includes subjecting the yarn prior to being hydrolyzed to adjustment. The adjustment may include removing surface liquid from the yarn. The yarn may be rinsed with an aqueous solution before removing the surface liquid.

In some preferred embodiments, at least some of the polyphosphoric acid contained in the yarn is hydrolyzed. This can be achieved by heating the yarn. In certain embodiments, it is preferred to heat to a temperature of 150 ° C. or higher, 180 ° C. or higher, or 200 ° C. or higher. In some embodiments, the time to heat the yarn is within 1 minute. In another embodiment, the heating time of the yarn is set to 30 seconds or less.

According to the present invention, at least some of the polyphosphoric acid hydrolyzate is washed away from the yarn. Preferably, substantially all of the polyphosphoric acid hydrolyzate is washed away from the yarn. In some embodiments, the wash involves contacting the yarn with an aqueous base solution. In another aspect, the wash comprises contacting the yarn with an aqueous base solution followed by contact with an acid water soluble. Yet another suitable cleaning technique involves bringing the yarn into contact with water.

The additional cleaning technique involves contacting the yarn with water, base aqueous solution, water, acid aqueous solution and water in order, or contacting the filament with dilute acid aqueous solution, water, base aqueous solution, water, acid aqueous solution and water in order. Including that.

In a preferred particular embodiment, the yarn is dried to a water content of less than about 20 weight percent.

In some respects, the present invention applies the yarn to a temperature of about 400 ° C. or higher in step f). Regarding how to heat. In some embodiments, the temperature at which the yarn is dried is kept below 300 ° C.

In some embodiments, the yarn is collected at a speed of at least about 100 meters per minute. In another aspect, the yarn is collected at a speed of at least about 250 meters per minute, or at least about 500 meters, or at least about 800 meters.

In the method of the present invention, a solution that is a liquid crystal solution is preferably used.

The polyarene azole in a preferred specific embodiment is a rigid rod polymer.

Some suitable azole-forming recently include 2,5-dimercapto-p-phenylenediamine, terephthalic acid, bis- (4-benzoic acid), oxy-bis- (4-benzoic acid). Acid), 2,5-dihydroxyterephthalic acid, isophthalic acid, 2,5-pyridodicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,6-quinolindicarboxylic acid, 2,6-bis (4-carboxyphenyl) Includes pyridobisimidazole, 2,3,5,6-tetraaminopyridine, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, 2,5-diamino-4,6-dithiobenzene or any combination thereof .. The azole-forming monomers in some embodiments are 2,3,5,6-tetraaminopyridine and 2,5-dihydroxyterephthalic acid. The azole-forming monomer in some preferred methods is in the form of a complex of 2,3,5,6-tetraaminopyridine and 2,5-dihydroxyterephthalic acid.

The polyarene azole in some embodiments of the present invention is poly {2,6-diimidazo [4,5-b: 4', 5'-e] pyridinylene-1,4- (2,5-dihydroxy) phenylene}. is there.

Detailed description of specific aspects The present invention may be more easily understood by reference to the following detailed description in connection with the accompanying drawings and examples that form part of the present disclosure. The present invention is not limited to the specific devices, methods, conditions or parameters described and / or shown herein and the terms used herein are merely examples to describe individual embodiments. It should be understood that it is a term used in and should not be construed as a limitation of the claimed invention.

The singular forms "a," "an," and "the" as used herein, including the appended claims, include the plural, and references to specific numbers are clearly indicated in the text in other forms. Unless otherwise included, at least that particular value is included. Another aspect of indicating a range of values includes from one particular value to / or another particular value. Similarly, when the value is expressed as an approximation using the antecedent "about", it will be understood that the particular value constitutes another aspect. The range is entirely inclusive and combinable. If any variable is present in any component or in any expression more than once, its definition in each entity is independent of its definition in all other entities. Combinations of substituents and / or variables are allowed only if such combinations result in stable compounds.

The following terms, as used above and throughout this disclosure, should be understood to have the following meanings, unless otherwise stated.

The filament of the present invention can be produced from a polyarene azole polymer. A "polyarene azole" as defined herein is a single heteroaromatic ring condensed with an adjacent aromatic group (Ar) [this is a repeating unit structure (a):

<chemistry num="1"><img file="JP4769293B2_D0001.tif" /></chemistry>

(Here, N is a nitrogen atom, and Z is a sulfur, oxygen or NR group, where R is a hydrogen or substituted or unsubstituted alkyl or aryl bonded to N). Or a common aromatic group (Ar)¹) And two heteroaromatic rings [this is a repeating unit structure (b1 or b2):

<chemistry num="2"><img file="JP4769293B2_D0002.tif" /></chemistry>

(Here, N is a nitrogen atom, and B is an oxygen, sulfur or NR group, where R is a hydrogen or substituted or unsubstituted alkyl or aryl bonded to N). Refers to a polymer having any of the above. The number of repeating unit structures represented by structures (a), (b1) and (b2) is not definitive. The number of repeating units for each polymer chain is typically from about 10 to about 25,000. Polyarene azole polymers include polybenzoazole polymers and / or polypyridazole polymers. Polybenzoazole polymers in certain embodiments include polybenzimidazole or polybenzobisimidazole polymers. Polypyridazole polymers in other particular embodiments include polypyridobis imidazole or polypyridoimidazole polymers. The polymer in a preferred particular embodiment is a polymer of the type polybenzobisimidazole or polypyridobis imidazole.

Y in structures (b1) and (b2) is an aromatic, complex aromatic, aliphatic or absent, preferably aromatic group, more preferably a 6-membered carbon atom. Even more preferably, the 6-membered aromatic group (Y) has two hydroxyl substituents in addition to the para-oriented bond, and even more preferably 2,5-. It is dihydroxy-para-phenylene.

Ar and Ar in structure (a), (b1) or (b2)¹Represent either aroma or complex aromatic groups, respectively.

The "aromatic" group may be a 5- to 13-membered single or dicarbonate aromatic ring, such as phenyl or naphthyl, which may optionally be substituted. Preferably, the group containing the aryl moiety is a monocyclic group having 5 to 6 carbon atoms in the ring. Phenyl is one suitable aryl.

A "complex aromatic" group as used herein is a 5- to 13-membered carbon-containing mono- or bicyclic aromatic having 1 to 5 heteroatoms (which may be independently nitrogen, oxygen or sulfur). ring It may be. Preferably, the heteroaryl moiety-containing group is monocyclic in which the number of members in the ring is 5 to 6 and 1 to 2 of the ring members are independently selected from nitrogen, oxygen or sulfur. is there. The repeating unit of the rigid rod polymer in a preferred embodiment essentially includes a structure with three heteroatoms, a pyridine-type ring at the center and a ring with two azoles. Pyridine-type rings are preferably monocyclic heteros having 5 to 6 members in the ring and 1 to 2 members of the ring independently selected from nitrogen, oxygen or sulfur. It is the azole part.

In some embodiments, the aryl or complex aromatic moieties may optionally be substituted, with the substituents being C.₁-C₆Alkyl, halogen, hydroxyl, C₁-C₆Alkoxy, CN, -NO₂, Amino, C₁-C₆Alkylamino, dialkylamino with 1-6 carbon atoms per alkyl group, thio, C₁-C₆Alkylthio, C₁-C₆Alkyl sulfinyl, C₁-C₆Alkylsulfonyl, C₂-C₇Alkoxycarbonyl, C₂-C₇Includes one or more of alkylcarbonyl, trifluoroalkoxy, benzylnitrile and benzoyl groups.

The aromatic or complex aromatic group may be either a suitable condensed or non-condensed polycyclic system, but in some embodiments it is preferably a single 6-membered ring. Ar or Ar in a particular embodiment¹The group is more preferably a complex fragrance in which one of the carbon atoms in the ring system is replaced by a nitrogen atom, or Ar or Ar.¹The ring atom contained in may be carbon only. Ar or Ar in yet another embodiment¹The group is more preferably a complex fragrance.

"Polybenzoazole" as defined herein is Ar or Ar.¹Refers to a polyarene azole polymer having a repeating structure (a), (b1) or (b2) in which the group is a single aromatic ring having 6 carbon atoms. The polybenzoazole is preferably a rigid rod-shaped polybenzoazole of the type represented by the structure (b1) or (b2), and more preferably a 6-membered carbocyclic aromatic ring Ar.¹The rigid rod-shaped polybenzoazole represented by the structure (b1) or (b2) having a structure (b1) or (b2) is included. Such suitable polybenzoazoles include, but are not limited to, polybenzimidazole (B = NR), polybenzothiazole (B = S), polybenzoxazole (B = O) and mixtures thereof or Contains copolymers. If the polybenzoazole is polybenzoimidazole, it is preferably poly (benzo [1,2-d: 4,5-d'] bisimidazole-2,6-diyl-1,4-phenylene). If the polybenzoazole is a polybenzothiazole, it is preferably poly (benzo [1,2-d: 4,5-d'] bistiazole-2,6-diyl-1,4-phenylene). If the polybenzoazole is a polybenzoxazole, it is preferably poly (benzo [1,2-d: 4,5-d'] bisoxazole-2,6-diyl-1,4-phenylene).

"Polypyridazole" as defined herein is Ar or Ar.¹Refers to a polyarene azole polymer having a repeating structure (a), (b1) or (b2) in which the group is a 6-membered single aromatic ring having 5 carbon atoms and 1 nitrogen atom. Such polypyridazoles are preferably rigid rod-like polypyridazoles of the type represented by structure (b1) or (b2), more preferably 6-membered heterocyclic aromatic rings Ar.¹The rigid rod-shaped polypyridazole represented by the structure (b1) or (b2) having a structure (b1) or (b2). Such more suitable polypyridazoles include, but are not limited to, polypyridobisimidazole (B = NR), polypyridobisthiazole (B = S), polypyridobisoxazole (B). = O) and mixtures or copolymers thereof are included. Even more suitable polypyridazole is a structure:

<chemistry num="3"><img file="JP4769293B2_D0003.tif" /></chemistry>

[Here, N is a nitrogen atom, R is hydrogen or substituted or unsubstituted alkyl or aryl bonded to N, preferably R is H] It is polypyridobisimidazole (B = NR) represented by. The average number of repeating units of the polymer chain is typically in the range of about 10 to about 25,000, more typically in the range of about 100 to 1,000, even more typically in the range of about 125 to 500, even more typical. The target is within the range of about 150 to 300.

The phrase "functional terminal polyarene azole oligomer" as used herein refers to a polyarene azole oligomer having at least one reactive group at the terminal position.

The term "oligomer" as used herein refers to a molecule having 2 to about 5 covalently bonded chemical units, which may be the same or different.

As used herein, the term "polymer" refers to a molecule that has more than about 5 covalently bonded chemical units, which may be the same or different.

As used herein, the term "alkyl" refers to a substituted or unsubstituted aliphatic hydrocarbon chain, which is not limited thereto, but preferably has 1 to 12 carbon atoms. Includes straight and branched chains with 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, i-butyl and t-butyl. Specifically, aliphatic hydrocarbon chains that may optionally be substituted are included within the definition of "alkyl." As used in the definitions herein, the number of carbon atoms refers to carbon backbones and carbon branches, not including substituents, such as carbon atoms such as alkoxy substituents.

In a particular embodiment of the invention, the substituents of the alkyl group include nitro, cyano, -N (R)._x) (R_y) [Here, R_xAnd R_yAre independently H, alkyl or aryl], halo, hydroxy, aryl, heteroaryl, alkoxy, alkoxyalkyl and alkoxycarbonyl.

Some aspects of the invention are directed towards polyarene azole filaments, more specifically polybenzoazole (PBZ) filaments or polypyridazole filaments, and methods of making such filaments. Other aspects further include yarns, fabrics and products incorporating the filaments of the invention, and methods of producing such yarns, fabrics and products.

When producing the filaments of the invention as used herein, a polyarene azole polymer, such as a polybenzoazole (PBZ) or a polypyridazole polymer, is used. For the purposes of this specification, the term "filament" refers to a relatively flexible, macroscopically uniform substrate with a high ratio of length to width across a cross-sectional region perpendicular to the length direction. The cross-sectional shape of the filament may be any shape, but is typically circular. The term "filament" may be used interchangeably with the term "fiber".

As defined herein, "yarn" refers to two or more fibers of continuous length, where the fibers are as defined above.

For the purposes of this specification, "fabric" refers to either a woven, knitted or non-woven structure. "Weaving" means any of the fabric weaves, such as plain weave, crowfoot weave, basket weave, satin weave, twill weave, and so on. "Knitting" means a structure produced by interlooping or intermeshing of one or more ends, fibers or multifilament yarns. "Non-woven" means a network of fibers, which includes unidirectional fibers, felt and the like.

In some embodiments, more suitable rigid rod-shaped polypyridazoles are described, but not limited to, homopolymers and copolymers of polypyridobis imidazole, such as US Pat. No. 5,674,969. Includes those that are. One such typical polypyridobisimidazole is the homopolymer poly (1,4- (2,5-dihydroxy) phenylene-2,6-diimidazole [4,5-b: 4'. , 5'-e] Pyridinylene). This polymer is also known in various terms, for example poly (1,4- (2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d: 5,6-d'] bis. Imidazole); Poly [(1,4-dihydroxyimidazole [4,5-b: 4', 5'-e] Pyridine-2,6-diyl) (2,5-dihydroxy-1,4-phenylene)]; Poly [(2,6-diimidazo [4,5-b: 4', 5'-e] pyridinylene- (2,5-dihydroxy-1,4-phenylene)]; Chemical Abstracts Registry No.167304-74-7, Poly [(1,4-dihydroxydiimidazo [4,5-b: 4', 5'-e] pyridine-2,6-diyl) (2,5-dihydroxy-1, 4-phenylene)]; 2,5-dihydroxyterephthalic acid-1,2,4,5-tetraaminopyridine copolymer; PIPD; pyridobisimidazole-2,6-diyl (2,5-dihydroxy-p-) Phenylene) copolymer; poly (1,4- (2,5-dihydroxy) phenylene-2,6-diimidazole [4,5-b: 4', 5'-e] pyridinylene) and poly (1,4-) It is also known as (2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d5,6-d'] bisimidazo).

The polyarene azole polymer used in the present invention may exhibit properties related to a rigid rod structure, a semi-rigid rod structure or a flexible coil structure, preferably a rigid rod structure. When this type of rigid rod polymer is represented by the structure (b1) or (b2), it is preferably the aromatic group Ar.¹It has two azole groups that are condensed with.

Suitable polyarene azoles useful for use in the present invention include homopolymers and copolymers. The amount of other polymeric material that can be mixed with the polyarene azole is no more than about 25 weight percent. It is also possible to use a copolymer containing about 25% or more of another polyarene azole monomer or another monomer instead of the main polyarene azole monomer. Proper polyarene azole homopolymers and copolymers can be prepared using known procedures, such as US Pat. No. 4,533,693 (Wolfe et al., August 6, 1985), US Pat. No. 4,703,103 (Wolfe). Others, October 27, 1987), US Pat. No. 5,089,591 (Gregory et al., February 18, 1992), US Pat. No. 4,772,678 (Sybert et al., September 20, 1988), US Pat. No. 4,847,350 (Gregory et al., September 20, 1988). Harris et al., August 11, 1992), US Pat. No. 5,276,128 (Rosenberg et al., January 4, 1994) and US Pat. No. 5,674,969 (Sikkema et al., October 7, 1997) (each quoted). This can be carried out using the procedures described in (which is incorporated herein by the whole) and the like. It is also possible to mix an additive such as an antioxidant, a lubricant, an ultraviolet blocking agent, a coloring agent, etc. with such a polyarene azole in a desired amount.

A suitable polyarene azole monomer is placed in a solution of a non-oxidizing, dehydrating acid and reacted in a non-oxidizing atmosphere with mixing while increasing the temperature in a stepwise or gradual ascending fashion. The polyarene azole polymer can be rigid rod-like, semi-rigid rod-like or flexible coil-like. It is preferably a liquid-leaving liquid crystal polymer, which forms a liquid crystal domain when its concentration exceeds the critical concentration in solution.

A specific aspect of the present invention provides a method for increasing the intrinsic viscosity of a polyarene azole polymer solution. This method typically adds an azole-forming monomer and an iron metal powder (the iron metal powder is added in an amount of about 0.05 to about 0.9 weight percent based on the total weight of the azole-forming monomer. ) Is put into polyphosphoric acid and brought into contact with the azole-forming monomer to react with each other to form a polyarene azole polymer. The azole-forming monomer is appropriately prepared individually in an aqueous solution in a reaction vessel and then precipitated to form a monomer complex. For example, one suitable method is to use the tank under a nitrogen purge and charge it with phosphate buffer (pH range from about 4.0 to about 4.5) and water. Heat the solution to about 50 ° C. Alkaline salt of 2,5-dihydroxyterephthalic acid and Na using the second tank under nitrogen purge₂S₂O₄And NH₄The combination of OH and water produces an aqueous solution of the azole-forming monomer, preferably 2,5-dihydroxyterephthalic acid (DHTA). A third tank is used to prepare an aqueous mixture of the second azole-forming monomer that can react with the first azole-forming monomer, preferably tetraaminopyridine (preferably in a tank under a nitrogen blanket). "TAP") 3HCl H₂NH after mixing O and water₄By adding some OH, TAP, 3HCl, H₂Produces a solution of O.

After transferring the solution in the third tank to the second tank, in some embodiments the pH is adjusted in the range of about 9 to about 10. Then, while blowing nitrogen into the combined solution, the solution is heated to about 50 ° C. until the solution becomes transparent while stirring the mixture. An amount of additional H sufficient to maintain the pH during the process of adding the clarified solution to the first tank to about 4.5.₃PO₄The monomer complex is precipitated by transfer with, thereby producing a slurry. The slurry containing the monomeric complex is typically filtered under nitrogen and then washed with water and degassed ethanol. The monomeric complex may be maintained in an inert atmosphere and dried prior to polymerization.

A better way to increase the intrinsic viscosity of the polyarene azole polymer solution is in an autoclave with 2,6-diamino-3,5-dinitropyridine (DADNP), water, a 5% Pt / C catalyst and water. It includes the hydrogenation of the DADNP by heating the ammonium oxide together under pressure. After exhausting and cooling, activated carbon is added to the autoclave as a slurry in water and then mixed. The solution is then filtered to give a colorless TAP solution. This is K₂-DHTA / Na₂S₂O₄Add to solution with stirring. After diluting the previously mixed phosphate buffer solution with water, it is placed in the compounding tank in advance and heated to about 50 ° C while mixing. Next, the basic TAP / K in the coupling tank₂-H while adding DHTA mixture (pH about 10)₃PO₄Add an aqueous solution to adjust the pH to about 4.5. During this addition, a large amount of bright yellow fine monomeric complex crystals are generated. The final pH is brought to about 4.5 while cooling the monomeric complex slurry. The slurry is then filtered to give a pale yellow cake. The monomeric complex cake is washed with water followed by ethanol and then left overnight while purging with nitrogen. The color of the final cake is pale yellow.

The polymerization of the monomer complex is typically carried out in a reaction vessel appropriately equipped with a connecting tool for purging the inert gas while applying a vacuum, heating and stirring. The reaction vessel is typically a monomeric complex, P.₂O₅, PPA and powdered metal are added. Typically, the reaction vessel is purged, heated and then mixed to cause polymerization. In one particularly preferred embodiment, about 20 parts of the monomer complex in a suitable reaction vessel, P.₂O₅About 10 parts, about 60 parts of polyphosphoric acid and about 0.1 parts of tin or iron metal. The contents of the reaction vessel are heated to about 100 ° C. for about 1 hour under vacuum with a slight nitrogen purge while stirring at about 60 rpm. Typically, the temperature is raised to at least 120 ° C, preferably at least about 130 ° C (preferably less than about 140 ° C) for a few more hours, preferably about 4 hours. The temperature is then raised to a higher temperature, at least about 150 ° C, more typically at least about 170 ° C, preferably about 180 ° C for about 1 hour, more preferably about 2 hours. Hold. Typically, the reaction vessel is flushed with nitrogen and then a sample of the polymer solution is taken and the viscosity is measured.

The method in some embodiments comprises: a) Azole-forming monomers, metal powders and optionally P₂O₅To form a mixture by contacting in polyphosphoric acid, b) Mix the mixture at a temperature of about 50 ° C to about 110 ° C and c) The mixture is further mixed at a temperature of about 144 ° C or less to produce a solution containing oligomers. d) The solution is degassed and e) React the solution of the oligomer at a temperature of about 160 ° C to about 250 ° C for a sufficient time to form a polymer. Consists of that.

The relative molecular weight of such a polyarene azole polymer is appropriately adjusted after diluting the polymer product with an appropriate solvent such as methanesulfonic acid to bring the polymer concentration to 0.05 g / dl. Characterize by measuring the viscosity of one or more dilute solutions at 30 ° C. The molecular weight evolution exhibited by the polyarene azole polymers of the present invention is appropriately monitored and interrelated by measuring the viscosity of one or more dilute solutions. Therefore, the relative viscosity of the dilute solution (V is typically used for the purpose of monitoring the molecular weight of the polymer._relOr "η"_relOr "n_rel) And intrinsic viscosity V_inhOr "η"_inhOr "n_inh) Use the measured value. The formulas for the relative viscosity and intrinsic viscosity of the dilute polymer solution are V_inh= ln (V_rel) / C [In the equation, ln is the natural logarithm function, and C is the concentration of the polymer solution] It is related according to. V_relIs the unitless ratio of the viscosity of the polymer solution to the viscosity shown when the polymer is solvent-free, and therefore V._inhIs a unit of reverse concentration, typically 1 Expressed as deciliters per ram (dl / g). Therefore, in a particular aspect of the invention, the intrinsic viscosity at 30 ° C. when the polymer is placed in methanesulfonic acid at a concentration of 0.05 g / dl is characterized as resulting in a polymer solution of at least about 22 dl / g. It gives rise to a polyarene azole polymer. Increasing the molecular weight of the resulting polymer disclosed herein results in a viscous polymer solution, so it is advisable to add the polymer to methanesulfonic acid at a concentration of approximately 0.05 dl / g. It is useful for measuring the intrinsic viscosity in a reasonable amount of time.

It is useful to use different types of metal powders in different amounts to help establish the molecular weight of polyarene azoles. In certain methods, it is particularly preferred that the iron metal powder be present in an amount of about 0.1 to about 0.5 weight percent relative to the monomer. A suitable iron metal powder would be, in particular, a fine powder having sufficient surface area to catalyze the polymerization reaction. In this regard, the particle size of the iron metal powder should be appropriately set so that it passes through a 200 mesh screen.

Suitable for azole-forming monomers, 2,5-dimercapto-p-phenylenediamine, terephthalic acid, bis- (4-benzoic acid), oxy-bis- (4-benzoic acid), 2,5- Dihydroxyterephthalic acid, isophthalic acid, 2,5-pyridodicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,6-quinolindicarboxylic acid, 2,6-bis (4-carboxyphenyl) pyridobisimidazole, 2, Includes 3,5,6-tetraaminopyridine, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, 1,4-diamino-2,5-dithiobenzene or any combination thereof. Preferably, the azole-forming monomer contains 2,3,5,6-tetraaminopyridine and 2,5-dihydroxyterephthalic acid. In certain embodiments, it is preferred that the azole-producing monomer undergo phosphoric acidation. Preferably, the phosphorylated azole-forming monomer is polymerized in the presence of polyphosphoric acid and a metal catalyst.

The azole-producing monomer may be selected to produce any of a variety of polyarene azoles, but suitable polyarene azoles produced according to certain aspects of the methods of the invention include polypyridazoles. , This preferably comprises polypyridobisimidazole, which preferably contains poly (1,4- (2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d: 5]. , 6-d'] Bisimidazole) is included.

The monomer is selected to produce any of a variety of polyarene azoles, but suitable polyarene azoles produced according to certain aspects of the methods of the invention include polybenzoazoles, which are preferred. Includes polybenzobisazole.

In some embodiments, the invention also provides a method for producing a polyarene azole polymer. The method appropriately comprises azole-forming monomers and metal powders, which include tin metals, iron metals, vanadium metals, chromium metals or any combination thereof. Including the step of reacting the monomer to form a polyarene azole polymer by putting (adding in an amount of about 0.05 to about 0.9% by weight based on the total amount of the dimer) into polyphosphoric acid and contacting them. To do. Typically, this method is adequately characterized as having an intrinsic viscosity at 30 ° C. resulting in a polymer solution of at least about 22 dl / g when the polymer is placed in methanesulfonic acid at a concentration of 0.05 g / dl. Produces polyarene azoles. In certain embodiments, the metal powder is present in an amount of about 0.1 to about 0.5 weight percent relative to the monomer. Suitable metal powders are fine particle size powders with a high surface area suitable for catalyzing the polymerization reaction. Therefore, a suitable metal powder particle size is such that it passes through a 200 mesh screen. By polymerizing similar monomers according to such a method, a polymer produced using the method as described above can be obtained. It is also possible to cause it.

Also provided is a method for producing a monomer complex containing 2,3,5,6-tetraaminopyridine (TAP) and 2,5-dihydroxyterephthalic acid (DHTA) monomer. The method in this embodiment typically involves contacting a molar excess of 2,3,5,6-tetraaminopyridine free base with dipotassium 2,5-dihydroxyterephthalate in water to form an aqueous mixture. Includes the step of precipitating the monomeric complex by adjusting the pH of the aqueous mixture in the range of about 3 to about 5. In certain embodiments, the molar ratio of 2,3,5,6-tetraaminopyridine free base to dipotassium 2,5-dihydroxyterephthalate is more typically at least about 1.05 to 1, and even more typically at least. From about 1.075 to 1, especially at least about 1.15 to 1.

The pH of the reaction mixture is appropriately maintained by adding an acid, preferably orthophosphoric acid, to the aqueous mixture. In various embodiments, suitable salts include alkaline salts of 2,5-dihydroxyterephthalic acid and ammonium salts of 2,5-dihydroxyterephthalic acid. The alkaline salt of 2,5-dihydroxyterephthalic acid is preferably a dipotassium salt of 2,5-dihydroxyterephthalic acid.

The pH of the aqueous mixture is typically adjusted so that the monomeric complex precipitates. Suitable pH for precipitating the monomeric complex is in the range of about 4.3 to about 4.6. Specific aspects of the invention after generating the monomeric complex also include one or more additional steps of polymerizing the monomeric complex to produce a polyarene azole. In this aspect, any of the monomers as described herein can be used to generate any of the polyarene azoles. For example, in certain embodiments, poly (1,4) is a polyarene azole using a monomer complex composed of 2,3,5,6-tetraaminopyridine and a 2,5-dihydroxyterephthalic acid monomer. -(2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d: 5,6-d'] bisimidazole) is produced.

Also, in some embodiments, a poly (1,4- (2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d: 5,6-d'] bisimidazole) polymer is produced. This polymer has an intrinsic viscosity at 30 ° C of at least about 22 dl / g, more typically at least about 25 dl / g, and even more, when the polymer concentration is 0.05 g / dl with methanesulfonic acid. It is typically characterized as yielding a polymer solution of at least about 28 dl / g, and more typically at least about 30 dl / g. In various aspects of the invention, the poly (1,4- (2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d: 5,6-d'] bisimidazole) polymer. Also includes filaments that can be manufactured using. For example, a polymer dope solution is extruded or spun through a die or spinneret to dope. Filament) may be produced or it may be spun. The spinneret preferably includes a large number of holes. The number of holes in such a spinneret and their arrangement are not decisive for the present invention, but it is desirable to maximize the number of holes for economic reasons. The number of holes included in the spinneret may be from about 100 to 1000 or more, and they may be arranged in any of a circular, grid or other desired arrangement. The spinneret may be made of any material that is not degraded by the dope solution. Also provided in various embodiments are multifilaments comprising a large number of filaments. The number of filaments per multifilament yarn is approximately the number of holes in the spinneret. The yarn tensile strength exhibited by the multifilaments produced using the filaments of the present invention is typically at least about 24 grams (gpd) per denier.

Also, additional poly (1,4- (2,5-dihydroxy) phenylene-2,6-pyrido [ A method for producing a 2,3-d: 5,6-d'] bisimidazole) polymer is also provided. In this embodiment, a molar excess of 2,3,5,6-tetraaminopyridine free base is contacted with 2,5-dihydroxyterephthalate in water to form an aqueous mixture, the pH of the aqueous mixture being about 3 By adjusting to the range of about 5, the monomer complex composed of 2,3,5,6-tetraaminopyridine and 2,5-dihydroxyterephthalic acid monomer is precipitated, and the above-mentioned single amount is prepared. The monomer composite is brought into contact with a metal powder in polyphosphate (the metal powder is added in an amount of about 0.05 to about 0.9 weight percent based on the total weight of the monomer composite). It includes producing a polymer solution by polymerizing the body in polyphosphoric acid. In certain aspects of these embodiments, the molar ratio of 2,3,5,6-tetraaminopyridine to 2,5-dihydroxyterephthalic acid is typically at least about 1.05 to 1, more typically at least about. From 1.075 to 1, and even more typically at least about 1.15 to 1. In a particular aspect of these embodiments, the pH is appropriately adjusted by adding an acid, such as orthophosphoric acid, to the aqueous mixture. Appropriately, the equivalent P that the polyphosphoric acid shows after polymerization₂O₅The content is typically at least about 81 weight percent, more typically at least about 82 weight percent. Corresponding P in certain embodiments₂O₅The content should be at least about 83 weight percent, and in other embodiments at least 87 weight percent. The metal powder appropriately includes iron powder, tin powder, vanadium powder, chromium powder or any combination thereof. Such a metal powder is preferably iron powder. In a specific embodiment of these embodiments, the 2,5-dihydroxyterephthalate is an alkali salt or an ammonium salt of 2,5-dihydroxyterephthalic acid, and preferably the alkali salt is dipotassium 2,5-dihydroxyterephthalate. It is salt. In additional embodiments, the method may further include one or more additional steps that result in the product, such as filaments and yarns. Therefore, the present invention also uses certain spinning methods or fiber spinning methods to poly (1,4- (2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d: 5,6-d]. It also provides an additional step of producing fibers from the polymer solution (ie, dope) produced by putting ('] bisimidazole) in polyphosphoric acid. Add 0.05 g / dl of poly (1,4- (2,5-dihydroxy) phenylene-2,6-pyrido [2,3-d: 5,6-d'] bisimidazole) polymer to methanesulfonic acid. The measured intrinsic viscosity of the solution produced in is preferably at least about 22 dl / g when it is placed in methanesulfonic acid at 0.05 g / dl and measured at 30 ° C.

A specific aspect of the present invention will be considered with reference to FIG. In some embodiments, the polymer is formed in a solvent that is an acid to give the dope solution 2. In another embodiment, the polymer is formed and then dissolved in a solvent that is an acid. Both are within the scope of the present invention. Preferably, the polymer is generated in a solvent that is an acid and then used in the present invention. The dope solution 2 containing the polymer and polyphosphoric acid contains the polymer at a concentration high enough to form a filament 6 that is typically accepted after the polymer is extruded and solidified. When the polymer is a liquid-releasing liquid crystal, the concentration of the polymer in the dope 2 is preferably increased sufficiently to cause the liquid crystal dope. The polymer concentration is preferably at least about 7 weight percent, more preferably at least about 10 weight percent, and most preferably at least about 14 weight percent. The maximum concentration is typically selected primarily by practical factors such as the solubility of the polymer and the viscosity of the dope. The concentration of the polymer is preferably 30% by weight or less, more preferably about 20% by weight or less.

Additives such as antioxidants, lubricants, UV blocking agents, colorants and the like may be added to the polymer-doped solution 2, and usually they are added.

The polymer dope solution 2 is typically extruded or spun through a die or spinner 4 to produce or spin the dope filament 6. The number of holes included in the spinneret 4 is preferably large. The number of holes in the spinneret and their arrangement are from the main Although not decisive for Ming, it is desirable to maximize the number of holes for economic reasons. The number of holes to be included in the spinneret 4 may be from about 100 to 1000 or more, and they may be arranged in any of a circle, a grid or other desired arrangement. The spinneret 4 may be made of any material that is not deteriorated by the dope solution 2.

When spinning fibers with solutions, a significant number of methods can be used, however, wet spinning and "air gap" spinning are best known. The general arrangement of spinning caps and baths suitable for such spinning methods is well known in the art and is described in US Pat. Nos. 3,227,793, 3,414,645, 3,767,756 and 5,667,743 (each by reference as a whole). Is incorporated herein) to illustrate how high-strength polymers are so spun. In "air gap" spinning, the fibers are typically first passed through a spinneret and extruded into a gas, such as air. Using FIG. 1 to help illustrate a method using "air gap" spinning (sometimes also known as "dry jet" wet spinning), the dope solution 2 from the spinneret 4 is in a very short time. There is, but it goes into the gap 8 between the spinneret 4 and the coagulation bath 10 (which does not necessarily have to be airy, but is typically referred to as the "air gap"). The fluid placed in the gap 8 may be any fluid that does not induce coagulation or adversely react with the doping, such as air, nitrogen, argon, helium or carbon dioxide. May be good. The dope filament 6 is stretched by passing through the air gap 8 with or without stretching, and then immediately enters the liquid coagulation bath solution. Alternatively, the fiber can be subjected to "wet spinning". In the case of wet spinning, the fibers are typically extruded through a spinning spout and then directly into the coagulation bath liquid, but the spinning spout is generally immersed in the coagulation bath liquid. Or position it below the liquid level. Any spinning method can be used when producing the fibers used in the method of the present invention. In some aspects of the invention, air gap spinning is preferred.

The filament 6 is "coagulated" in a coagulation bath 10 containing water or a mixture of water and phosphoric acid, thereby allowing the filament 6 to substantially stretch polyphosphate during any of the following steps: Remove enough to disappear. When extruding a large number of fibers at the same time, the multifilament yarn may be produced by combining them before, during and after subjecting them to a solidification step. The term "coagulation" as used herein does not necessarily mean that the dope filament 6 is a fluid and changes to a solid phase. The temperature of the dope filament 6 may be so low that it essentially does not flow before it enters the coagulation bath 10. However, the coagulation bath 10 ensures or completes the coagulation of the filament, i.e. changes the polymer from the dope solution 2 to a substantially solid polymer filament 12. The amount of solvent removed during this coagulation step, namely polyphosphoric acid, will depend on the time the filament 6 is in the coagulation bath, the temperature of the bath 10 and the concentration of solvent in it. .. For example, when a 20 weight percent phosphoric acid solution is used at a temperature of about 23 ° C, a residence time of about 1 second will remove about 70 percent of the solvent present in filament 6.

Typically, for the purpose of preserving the fibrous properties of the polymer, the polyphosphoric acid remaining associated with the filament is substantially hydrolyzed and then removed. Usually, the filament or yarn is heated followed by a wash and / or neutralization step to allow the PPA to hydrolyze. One hydrolysis mode involves convective heating of the coagulated fibers for a short period of time. As an alternative to convection heating, it is also possible to cause hydrolysis by placing a moist filament or yarn in a coagulated state in boiling water or an aqueous acid solution and heating it. Such treatment causes the PPA to hydrolyze while maintaining sufficient tensile strength of the product fiber. Such heat treatment steps may be performed in separate cabinets 14, or may be performed in the first step order followed by a step of performing cleaning more than once in the existing cleaning cabinet 14. May be good. In some embodiments, it is (a) hydrolyzed to PPA by causing contact between the dope filament and the solution in a bath or cabinet 14, and then (b) the filament and neutralizing solution. Contact with water in a bathtub or cabinet 16 containing an effective amount of base under conditions sufficient to neutralize the phosphoric acid, polyphosphoric acid or any combination thereof contained in the filament in a sufficient amount. It will be solved by waking it up.

After performing a treatment in which the PPA associated with the coagulated filament undergoes substantial hydrolysis, the filament or yarn 12 is washed in one or more washing steps to provide the residual acid solvent / and / or PPA. The PPA hydrolyzate may be removed from the filament or yarn 12 by removing most of the hydrolyzate from the filament or yarn 12. The filament or yarn 12 is washed multiple times with water before and / or after the filament or yarn 12 is treated with a base or the filament or yarn is treated with a base. It is also possible to carry out at. Further, it is also possible to reduce the concentration of the cation contained in the polymer by subjecting the filament or yarn to a treatment with an acid thereafter. The series of washes can be performed as a continuous process by passing the filament through a series of bathtubs and / or one or more cleaning cabinets. FIG. 1 shows a type of cleaning tub or cabinet 14. The cleaning cabinet typically comprises a sealed cabinet containing one or more rolls, the filament moving around and crossing the rolls multiple times before exiting the cabinet. As the filament or yarn 12 is moving around the roll, it is sprayed with a cleaning fluid. The cleaning fluid is continuously collected at the bottom of the cabinet and then drained.

The temperature of one or more cleaning fluids is preferably 30 ° C or higher. It is also possible to add the cleaning fluid in the gas form (steam), but more conveniently, it is used in the liquid form. Preferably, a large number of cleaning tubs or cabinets are used. The time that the filament or yarn 12 resides in any one cleaning tub or cabinet 14 depends on the desired residual phosphorus concentration in the filament or yarn 12, but preferably the residence time is from about 1 second to about. Within 2 minutes. In the case of a continuous process, the total cleaning process time in a large number of suitable cleaning tubs and / or cabinets is preferably within about 10 minutes, more preferably from about 5 seconds or more to about 160 seconds.

In some embodiments, suitable bases for removing PPA hydrolyzate include NaOH, KOH, Na.₂CO₃, LVDS₃, K₂CO₃, KHCO₃Or trialkylamines, preferably tributylamines or mixtures thereof. The base in one embodiment is water soluble.

In the step after treating the fiber with a base, optionally, a step of contacting the filament with a cleaning solution containing water or acid so that all or substantially all of the excess amount of base is removed. May be included. The cleaning solution may be added into the cleaning tub or cabinet 18.

Water and other liquids may be removed by drying the fibers or yarns 12 in a dryer 20. The temperature inside the dryer is typically from about 80 ° C to about 130 ° C. The residence time in the dryer is typically from 5 seconds to about 5 minutes when the temperature is lowered. The atmosphere of the dryer may be nitrogen or other non-reactive atmosphere. Next, the fiber may be subjected to further treatment, for example, in the thermosetting device 22 or the like. Further processing may be performed in the nitrogen purge tube furnace 22 to increase the tensile strength of the filament and / or release the physical strain of the molecule. Finally, the filament or yarn 12 is wound by the take-up device 24 into a package. Properly position rolls, pins, guides and / or power 26 for the purpose of transferring the filament or yarn throughout the process.

The phosphorus content of the filament dried after removing the PPA hydrolyzate is preferably less than about 5,000 ppm (0.5%) by weight, more preferably less than about 4,000 ppm (0.4%) by weight, most preferably about. Try to be less than 2,000ppm (0.2%) weight.

Typically, the yarns are collected at a speed of at least 50, or at least 100, or at least 250, or at least 500, or at least 800 meters per minute.

In some embodiments, the present invention relates to a method for the continuous production of a polyarene azole multifilament, which method is: a) A large number of filaments are produced by extruding a solution containing a polyarene azole polymer and polyphosphoric acid through a large number of orifices. b) Generate multifilament yarn from the filament c) By heating the yarn to a temperature of about 120 ° C or higher for about 2 minutes or less, at least some of the polyphosphoric acid contained in the yarn is hydrolyzed. d) Rinse at least some of the polyphosphoric acid hydrolyzate from the yarn. e) Dry the washed yarn and f) In some cases, heat the yarn above about 300 ° C and g) Collect the yarns at a speed of at least about 50 meters per minute, Consists of that.

In certain embodiments, the method additionally includes adjusting the yarn before subjecting it to hydrolysis.

In some embodiments, the filament is extruded and then passed through an air gap and then into a coagulation bath.

[Example] The terms "mmol" and "mmol" as used herein are synonymous. Solid concentration of polymer, weight percent based on monomer and P of polymer solution₂O₅The entire percentage of concentration is expressed relative to the TD-complex as a complex of 1: 1 mol of TAP and DHTA (the TD-complex is considered monohydrate).

In the following examples, the test method described below was used.

Measure in degrees Celsius (° C) unless otherwise specified.

Denier is measured according to ASTM D 1577, which is the linear density of fibers as expressed as the weight (grams) of fibers at 9000 meters.

Tensile strength is measured according to ASTM D 3822, which is the maximum or breaking stress of the fiber as expressed as the force per unit of cross-section.

Elemental analytical values of alkaline cations (M) and phosphorus (P) are measured according to the inductively coupled plasma (ICP) method described below. Place the accurately weighed sample (1-2 grams) in the quartz container of the CEM Star 6 microwave device. After adding concentrated sulfuric acid (5 ml), moisten by swirling. After connecting the cooler to the container, the sample is decomposed using an appropriate carbonization method. This method involves carbonizing the organic material by heating the sample to various temperatures below 260 ° C. The device is used to automatically add a fixed amount of nitric acid at various decomposition stages. The clear final liquid decomposition product is cooled to room temperature and then diluted to 50 ml with deionized water. The solution can be analyzed using a Perkin Elmer optima inductively coupled plasma device under the conditions and settings recommended by the manufacturer. A total of 26 different elements can be analyzed using several different wavelengths per sample. For certain elements, such as sodium and phosphorus, a 1/10 dilution may be required. The calibration standard is 1 to 10 ppm.

Many of the examples below are provided for the purpose of exemplifying various aspects of the invention and should by no means be construed as limiting. All parts and percentages are weight unless otherwise stated. Examples of monomeric complexes

This example shows the use of 2,3,5,6-tetraaminopyridine (TAP) in a 5 percent molar excess when producing the monomeric complex by batch method. The water was degassed and deionized.

85% H under nitrogen purge in the first 2 liter agitated resin tank₃PO₄After charging 50 ml of water and 450 ml of water, a 10 wt% sodium hydroxide solution was added until the pH of the material in the tank was measured with a pH probe to about 4.6. The solution was heated to about 50 ° C.

Dipotassium salt of 2,5-dihydroxyterephthalic acid in a second 2 liter agitated resin tank ("K"₂-DHTA ") (41.1g) and 1g Na₂S₂O₄And 60g NH₄A solution of 2,5-dihydroxyterephthalic acid (DHTA) was produced by combining OH and 700 g of water under a nitrogen purge. The K₂-DHTA and Na₂S₂O₄Weighing was first performed in the glove box.

700g of water and 42g of TAP / 3HCl / H in a quart bottle with a septum₂By combining O (under a nitrogen blanket), TAP, 3HCl, H₂O solution was generated. Next, NH₄60 g of OH was added. The solution was cannulated into the second resin tank. The pH of the solutions combined in this second tank was about 9-10. The combined solution was heated to about 50 ° C while stirring and blowing nitrogen into it until the solution became clear. Add the solution to the first resin tank in an amount sufficient to adjust the pH to 4.5.₃PO₄The slurry was generated by transferring with a cannula and precipitating the monomeric complex. 50ml 85% H₃PO₄By diluting with 500 ml of water₃PO₄A solution was produced.

After filtering the slurry containing the monomeric complex under nitrogen, twice with 200 ml of water (6-8 grams of water per gram of wet product slurry) and 10 ml of degassed ethanol ( Washed with ~ 1 gram of ethanol per gram of wet product). The monomer complex was dried overnight by steam heating while being kept under nitrogen, and then recovered in a glove box in a nitrogen atmosphere.

Polymerization (Examples of using TAP in a monomer complex formulation in excess of 5.0% molar). A clean, dried, 200 ml glass tubular reactor [with an inner diameter of 4.8 cm, equipped with the fittings needed for nitrogen purging and vacuuming, with a heating jacket around it, In addition, a double-helix basket-type stirrer was placed], and 23.00 g of the monomer complex was added to P₂O₅11.24g, polyphosphoric acid ("PPA") (P₂O₅66.29g (% of which corresponds to 85.15%) and 0.115g of Sn were charged. The contents were heated to 100 ° C. for 1 hour under vacuum with a slight nitrogen purge while stirring at 60 rpm. The temperature was raised to 137 ° C and held for 4 hours. The temperature was raised to 180 ° C and held for 2 hours. The reaction vessel was flush-washed with nitrogen, the sample of the polymer solution was diluted with methanesulfonic acid to a concentration of 0.05%, and then the intrinsic viscosity n measured at 30 ° C._inhWas 23 dl / g.

The procedure of Example 1 was repeated, however, TAP · 3HCl · H₂By using 43 grams of TAP to generate the O solution, the molar excess of TAP was 7.5% compared to the molar excess of TAP of 5% as shown in Example 1.

Polymerization (Examples of using TAP in a monomer complex formulation in excess of 7.5% molar). A clean, dried, 200 ml glass tubular reactor [with an inner diameter of 4.8 cm, equipped with the fittings needed for nitrogen purging and vacuuming, with a heating jacket around it, and more. , A basket-type stirrer with a double helix shape was placed], 20.00 g of the monomer complex, P₂O₅7.78g, PPA (P₂O₅59.52g (% of which corresponds to 85.65%) and 0.115g of Sn were charged. While rotating the stir bar at 100 rpm, slightly N the contents₂It was heated to 100 ° C. for 1 hour under vacuum with a purge. The temperature was raised to 137 ° C and held for 3 hours. The temperature was raised to 180 ° C and held for 2 hours. Nitrogen gas ("N"₂After flash washing with ), a sample of the polymer solution was diluted with methanesulfonic acid until the concentration reached 0.05%. n_inh= 28.5dl / g.

The procedure of Example 1 was repeated, however, TAP · 3HCl · H₂By using 46 grams of TAP to generate the O solution, the molar excess of TAP was 15% as compared to the molar excess of TAP of 5% as shown in Example 1.

Polymerization (Examples of using TAP in a monomeric complex formulation in excess of 15% molar). A clean, dried, 200 ml glass tubular reactor [with an inner diameter of 4.8 cm, equipped with the fittings needed for nitrogen purging and vacuuming, with a heating jacket around it, and more. , A basket-type stirrer with a double helix shape was placed], 20.00 g of the monomer complex, P₂O₅7.79g, PPA (P₂O₅59.54g (% of which corresponds to 85.65%) and 0.115g of Sn were charged. Some N while stirring the contents at 100 rpm₂It was heated to 100 ° C. for 1 hour under vacuum with a purge. The temperature was raised to 137 ° C and held for 4 hours. The temperature was raised to 180 ° C and held for 2 hours. The reaction tank is N₂After flash washing with, the polymer solution sample was diluted with methanesulfonic acid to a concentration of 0.05%. n_inh= 33.4dl / g.

This example shows the use of 2,3,5,6-tetraaminopyridine (TAP) in a 7.5 percent molar excess when producing the monomeric complex by the direct coupling method. 126.81g K in the tank₂-The dipotassium salt of 2,5-dihydroxyterephthalic acid (K) by combining DHTA with 2208 g of water and 2.2 grams of sodium dithioate.₂-DHTA / Na₂S₂O₄) A solution was produced.

In an autoclave 100.3 grams of 2,6-diamino-3,5-dinitropyridine (DADNP) and 508 grams of water and 2.04 grams of 5% Pt / C catalyst (on a dry basis) 1 gram of catalyst was used) and 10 grams of ammonium hydroxide were combined and heated to 65 ° C under 500 psig. Hydrogenation of the DADNP was completed in 2 hours. After exhaust and cooling to 30 ° C., about 15 g of Darco G60 activated carbon was added to 100 g of water as a slurry and mixed for 1 hour. The solution was filtered to remove the catalyst and then filtered through a single CUNO Biocap 30 54 SP filter. The filtration took 30 minutes, and the color of the filtered solution was clear throughout the transfer.

The colorless TAP solution was added to the K₂-DHTA / Na₂S₂O₄It was added to the solution with mixing at 50 ° C. That K₂-DHTA / Na₂S₂O₄The color of the solution was slightly yellow and did not change during the addition of the TAP, its TAP / K₂The pH of the -DHTA mixture was 10.0. Next, add 100 g of H to the clave and filter.₂Rinse with O and add it to the tank. The theoretical amount of TAP that could be generated, filtered and transferred to the mixing tank [including DADNP purity (98%)] was 68.8 g (0.494 mol), resulting in TAP / K.₂The maximum molar ratio of -DHTA was 1.075.

Dilute 150 ml of premixed phosphate buffer solution (pH = 4.7) with 600 ml of water, pre-charge in a compounding tank and heat to 50 ° C while mixing. did. Basic TAP / K in the compounding tank₂-25% H for the purpose of adjusting the pH to about 4.5 at the same time as adding the DHTA mixture (pH = 10)₃PO₄Aqueous solution was added. Almost immediately, a large amount of bright yellow fine monomeric complex crystals were formed and increased during the addition. The final pH was adjusted to 4.5 while cooling the slurry of the monomer complex to 30 ° C. The slurry was filtered to give a pale yellow cake. The cakes of the monomeric complex were washed with 400 g of water three times followed by 200 g of ethanol and then placed overnight under a nitrogen purge wash. The color of the cake was pale yellow.

Example A: In this example, the effect of producing the monomeric complex using TAP and DHTA in a ratio of 1: 1 is shown. A clean, dried 2CV Model DIT Mixer [available from Design Integrated Technology, Inc (Warrenton, Virginia)] was constantly purged with nitrogen gas, with the following in it: a) P₂O₅62.4g of polyphosphoric acid (PPA) with a concentration of 84.84%, b) P₂O₅The 14.71 grams, c) Tin powder [325 mesh, available from VWR scientific; take 0.5% of this amount based on the weight of the TD-complex, or 0.01421 mmol tin per 1 mmol of the TD-complex] to 0.11 g, and d) 22.89 grams of TD-complex [a 1: 1 complex of tetraaminopyridine (TAP) and dihydroxyterephthalic acid, ie 47.21 g TAP and 67.21 g DHTA].

The CV Model is a bipyramid reaction vessel with a jacket, which is heated by circulating hot oil in the jacket. The reaction vessel used double helix conical blades that intersected each other over the entire conical envelope of the bowl. The blade of the mixer was started and set to about 53 rpm. Anhydrous N in the reaction vessel₂Cleaned with gas. The temperature of the reaction mixture was measured with a thermocouple throughout. The temperature of the reaction mixture was raised to 100 ° C and held for 1 hour. The temperature of the reaction mixture was raised to 137 ° C and held for 3 hours. The temperature of the reaction mixture was then raised to 180 ° C and kept under vacuum for 3 hours. The polymer solution was discharged into a glass container while purging the mixer with nitrogen. This polymer was taken out from the mixing device in a form in which the polymer was contained in PPA in a state where the solid amount was 18%. After removing the polymer sample from the solution, the polymer solid was diluted with methanesulfonic acid (MSA) to a concentration of 0.05%. The intrinsic viscosity of the polymer sample was 6 dl / g.

Metal powder examples. The following examples demonstrate the effects of tin (Sn), vanadium (V), chromium (Cr) and iron (Fe) metals as reducing agents during polymerization.

While constantly purging the clean, dried 2CV Model DIT Mixer with nitrogen gas, we put together the following in this: a) P₂O₅126.5g of polyphosphoric acid (PPA) with a concentration of 85.15%, b) P₂O₅26.82 grams, c) Tin powder [325 mesh, available from VWR scientific; take 0.5% of this amount based on the weight of the TD-complex, or 0.01421 mmol tin per 1 mmol of the TD-complex] to 0.23 grams, and d) TD-complex [Tetraaminopyridine (TAP) plus dihydroxyterephthalic acid 1: 1 complex, effectively 94.42 g TAP and 134.42 g DHTA, approximately 10% molar excess of TAP used during preparation ] To 45.78 grams.

An oil-heated CV Model bipyramid reactor with double-helical conical blades that intersect each other over the entire conical envelope of the bowl was used. After starting the blades of the mixer and setting it to 53 rpm, the reaction mixture was evacuated in such a way that foaming of the mixture during the reaction was suppressed. The temperature of the reaction mixture was measured with a thermocouple throughout. The temperature was raised to 100 ° C and held for 1 hour. The temperature was raised to 137 ° C and held for 3 hours. The temperature was then raised to 180 ° C and held under vacuum for 3 hours. The polymer solution was discharged into a glass container while purging the mixer with nitrogen. This polymer was taken out from the mixing device in the form of 18% of the polymer in PPA.

A sample of the resulting polymer solution was diluted with methanesulfonic acid (MSA) to a concentration of 0.05% solid polymer. The intrinsic viscosity of the resulting polymer sample was 23 dl / g. See Table 1.

The procedure of Example 5 was repeated using 0.01421 mmol of iron powder per 1 mmol of TD-complex. The measured intrinsic viscosity of the resulting polymer sample was 29 dl / g. See Table 1.

The procedure of Example 5 was repeated with 0.01421 mmol of vanadium and chromium powder per 1 mmol of TD-complex. The intrinsic viscosities of the polymer samples generated with vanadium and chromium were both 22 dl / g. See Table 1.

Example B Example 5 was repeated without using a metal for reduction. The resulting intrinsic viscosity was 9 dl / g. See Table 1.

Example C Reduction metals copper (Cu), nickel (Ni), manganese (Mn), boron (B), titanium (Ti), aluminum (Al), gallium (Ga), cobalt (Co) and zinc (Zn) Example 5 was repeated using. The results are shown in Table 2.

Example D Example 5 was repeated using the metal salts tin chloride and magnesium chloride as reducing agents instead of the metal powder. The results are shown in Table 3.

<tables num="1"><img file="JP4769293B2_D0004.tif" /></tables>

<tables num="2"><img file="JP4769293B2_D0005.tif" /></tables>

<tables num="3"><img file="JP4769293B2_D0006.tif" /></tables>

Optimized reducing agent during polymerization. While constantly purging the clean, dried 4CV Model DIT Mixer with nitrogen gas, we put together the following in this: a) P₂O₅643.94g of polyphosphoric acid (PPA) with a concentration of 84.79%, b) P₂O₅127.22 grams, c) 2.5 grams of tin powder [325 mesh, available from VWR scientific; make the amount of this tin powder about 1.09 weight percent based on the amount of TD complex], and d) TD complex [Tetraaminopyridine (TAP) plus dihydroxyterephthalic acid 1: 1 complex, effectively 94.42 g TAP and 134.42 g DHTA, approximately 10% molar excess of TAP used during preparation] The 228.84 grams.

The CV Model was an oil-heated bipyramid reaction vessel that used double-helical conical blades that intersected each other over the entire conical envelope of the bowl. After starting the blades of the mixer and setting it to 53 rpm, the reaction mixture was evacuated in such a way that foaming of the mixture during the reaction was suppressed. The temperature of the reaction mixture was measured with a thermocouple. The temperature was raised to 100 ° C and held for 1 hour. The temperature was raised to 135 ° C and held for 3 hours. The temperature was then raised to 180 ° C and held for 2 hours. The polymer solution was discharged into a glass container while purging the mixer with nitrogen. This polymer was taken out from the mixing device in the form of 18% of the polymer in PPA.

A sample of the resulting polymer solution was diluted with methanesulfonic acid (MSA) to a concentration of 0.05% solid polymer. The measured intrinsic viscosity of this sample was 27 dl / g, which is indicated as item 1 in Table 4. The above procedure was repeated with 0.8, 0.5, 0.3, 0.074 and 0% relative to the weight of the TD complex using tin. The tendency of intrinsic viscosity with respect to tin content is shown graphically in Fig. 2.

<tables num="4"><img file="JP4769293B2_D0007.tif" /></tables>

Textile spinning example

Polymerization with tin (spinning fibers with 10% molar excess of TAP). While constantly purging the clean, dried 4CV Model DIT Mixer with nitrogen gas, we put together the following in this: a) P₂O₅663.0 grams of polyphosphoric acid (PPA) with a concentration of 85.15%, b) P₂O₅112.5 grams, c) Tin powder [325 mesh, available from VWR scientific; make the amount of this tin powder about 0.5% by weight based on the amount of TD complex] 1.1 grams, and d) 230.0 grams of TD complex [a 1: 1 complex of tetraaminopyridine (TAP) and dihydroxyterephthalic acid, ie 94.45 g TAP and 134.45 g DHTA].

The 4CV Model is a jacketed bipyramid reactor [used by a double spiral conical blade that heats the jacket by circulating hot oil and intersects with each other over the entire conical envelope of the bowl. Has been]. After setting the blades of the mixer to 80 rpm, the reaction mixture was evacuated in such a way that foaming of the mixture during the reaction was suppressed. The temperature of the reaction mixture was measured with a thermocouple. The temperature of the reaction mixture was raised to 100 ° C and held for 1 hour. The temperature was raised to 135 ° C and held for 4 hours. The temperature was then raised to 180 ° C and held for 2 hours. The polymer solution was discharged into a glass container while purging the mixer with nitrogen. This polymer was taken out from the mixing device in the form of 18% of the polymer in PPA. A sample of the polymer solution was diluted with methanesulfonic acid to a concentration of 0.05%. The intrinsic viscosity of the resulting polymer was 26 dl / g.

Textile spinning. Spinning of a solution containing the polymerized polymer in polyphosphoric acid was performed using dry jet wet spinning technology and water as a coagulation medium, resulting in 250 holes with 90 micron diameter holes. Multifilament yarn was produced by passing it through a spinneret. The length of the air gap was set to 15 mm so that the spin draw ratio that occurs in the air gap was about 14. The bobbins of the multifilament yarn were washed in hot (50 ° C) water for 2 weeks before drying. The moist yarn was dried by passing it through a 170-inch long 4-section tube oven with nitrogen at a rate of 7 m / min under a tension of 890 g at 170 ° C. The resulting 373 denier yarn showed the following physical properties: tensile strength / elongation / tensile stress: 27.8gpd / 2.62% / 1345gpd.

Polymerization with Fe metal (spinning fibers with 10% molar excess of TAP). While constantly purging the clean, dried 4CV Model DIT Mixer with nitrogen gas, we put together the following in this: a) P₂O₅682.1 grams of polyphosphoric acid (PPA) with a concentration of 85.65%, b) P₂O₅89 grams, c) Iron powder [325 mesh, available from Sigma-Aldrich; make the amount of this Fe powder about 0.5% by weight based on the amount of TD complex] 1.15 grams, and d) 228.9 grams of TD complex [a 1: 1 complex of tetraaminopyridine (TAP) and dihydroxyterephthalic acid (DHTA), ie 94.45 g TAP and 134.45 g DHTA].

The 4CV Model was heated with hot oil, which used double helix conical blades that intersected each other over the entire conical envelope of the bowl. After starting the blades of the mixer and setting it to 80 rpm, the reaction mixture was evacuated in a manner such that foaming of the mixture during the reaction was suppressed. The temperature of the reaction mixture was measured with a thermocouple throughout. The temperature of the reaction mixture was raised to 100 ° C and held for 1 hour. The temperature was raised to 135 ° C and held for 4 hours. The temperature was then raised to 180 ° C and held for 2 hours. The polymer solution was discharged into a glass container while purging the mixer with nitrogen. This polymer was taken out from the mixing device in the form of 18% of the polymer in PPA. A sample of the polymer solution was diluted with methanesulfonic acid to a concentration of 0.05%. n_inhWas 24 dl / g.

Textile spinning. Spinning of a solution containing the polymerized polymer in polyphosphoric acid was performed using dry jet wet spinning technology and water as a coagulation medium, resulting in 250 holes with 90 micron diameter holes. Multifilament yarn was produced by passing it through a spinneret. The length of the air gap was set to 15 mm so that the spinning draw ratio occurring in the air gap was about 14. The bobbin of the multifilament yarn was washed in boiling water for 90 minutes, then soaked in 2 wt% active aqueous solution for 2 hours, then soaked in water for 2 hours, the water was replaced with fresh water twice, and then Soaked in 2 wt% aqueous acetic acid solution for 2 hours, then in fresh water for 2 hours, the water was replaced with fresh water twice. The washed yarn bobbins were placed in a damp plastic bag and stored in a tube oven until dry. 170 ° C the yarn It was dried by passing it through a tube oven with a length of 1 foot at a speed of 0.5 m / min while purging with nitrogen under a tension of 1000 g. The resulting 387 denier yarn showed the following physical properties: tensile strength / elongation / tensile stress: 25.9 gpd / 2.24% / 1398 gpd.

Polymer method 11,580 grams of polyphosphoric acid (PPA) (P)₂O₅84.7%) is sent from the weighing tank at 120 ° C to a 10 CV DIT Helicone mixer (the blades of the mixer were stopped so that the addition port was not hidden) in an atmosphere of 1 atm of nitrogen. .. After the PPA is placed in the mixer, the blades of the mixer are rotated at 40 rpm and jacket cooling water is started to cool the PPA to 70 ° C. When the PPA has cooled, the flow of water is stopped, and the blades of the mixing device are stopped so that the addition port is not hidden.

3400 grams of P₂O₅Anhydrous nitrogen (N)₂) Place in the transfer bin in the weighing chamber below. The nitrogen pressure of 1 atm (absolute) in the mixer is N.₂Equal to 1 atmosphere in the weighing chamber under the blanket. The P₂O₅Is transferred to the 10CV mixer, and then the transfer valve is closed. After starting the blade of the mixer, increase its speed to 40 rpm. After resuming water cooling, P₂O₅Is slowly applied in a vacuum while mixing in PPA to cause the mixture to be degassed. Adjust the water cooling so that the contents of the mixer are maintained at 75 (± 5) ° C. After reducing the pressure in the mixer to 50 mmHg, mixing is continued for another 10 minutes. Next, after stopping the flow of water, the blade of the mixing device is stopped so that the addition port is not hidden. N₂The pressure is set to 1 atm (absolute) by letting in.

Weigh 10174 grams of monomeric-complex and anhydrous N₂Place in the transfer bin in the lower weighing chamber. In addition, 51 grams of tin powder (about 325 mesh) and 25 grams of benzoic acid are weighed and individual N in the same weighing chamber.₂Place in a transfer vessel under the blanket.

The pressure of 1 atm (absolute) in the mixer is N₂Equal to 1 atmosphere in the weighing chamber under the blanket. After transferring the monomeric complex, tin and benzoic acid to the 10CV mixer, the transfer valve is closed. After starting the blade of the mixer, increase its speed to 40 rpm. Water cooling is resumed when the stirrer is started, and after the blades of the mixer reach a speed of 40 rpm, the monomeric complex, tin and benzoic acid are placed in the PPA mixture for 10 minutes. And mix. Next, the mixture is degassed by slowly applying a vacuum while continuing the mixing. Adjust the water cooling so that the contents of the mixer are maintained at 75 (± 5) ° C. After reducing the pressure in the mixer to 50 mmHg, mixing is continued for 10 minutes. The speed of the blades of the mixer is then reduced to 12 rpm and the cooling water is reduced to raise the temperature of the contents in the mixer to 85 (± 5) ° C. Next, the blade of the mixing device is stopped, and N₂After the pressure is reduced to 1 atm, the contents of the mixer are transferred to a feed tank (DIT 10SC mixer) equipped with two stirrers.

The reaction mixture in the feed tank is maintained at a temperature of 110 ° C and an absolute pressure of 50 mmHg. Rotate both stirrers at 40 rpm. After raising the temperature of the mixture to 137 ° C by pumping the reactant mixture from the tank through a heat exchanger at an average rate of 10,050 grams / hour, a set of three static mixers. Oligomers are produced by placing them in the mold reaction vessel so that the residence time is 3 hours. Super Phosphoric Acid (SPA) (P) in the oligomer mixture coming out of the static mixing device type reaction vessel₂O₅76%) is injected at an average rate of 1079 grams / hour.

The oligomer mixture and SPA are then thoroughly mixed in a static mixer and then transferred to a agitated surge tank to remove any volatiles present in vacuum. The agitated surge tank is a DIT 5SC mixer, which maintains its temperature at 137 ° C. The average residence time in the surge tank is set to 1.25 hours.

Polymerization of the mixture The oligomer mixture is then further polymerized at a temperature of 180 ° C to achieve the desired molecular weight. The oligomer mixture is first pumped through a heat exchanger to raise the temperature of the mixture to 180 ° C and then into the polymerization solution for 5 seconds.^-1It is passed through the reaction tank system of the rotary Couette type shear reaction tank and the static mixing device that gives the shear rate of. The reaction tank system is maintained at 180 ° C (± 5) ° C and the residence time in this reaction tank system is set to 4 hours. Obtain a solution containing a polymer with an intrinsic viscosity of 25 dl / g.

Spinning method Fiber molding and quenching Next, using a gear pump for the purpose of increasing the pressure, a polymer with an IV of 25 was added to PPA (P).₂O₅The solution produced by adding 18% by weight to (has a concentration corresponding to 81.5%) is sent to the spinning machine. Next, a part of the solution is weighed and passed through a 5cc / 1 rotation gear pump at 180 ° C. The polymer solution is pumped through a spinneret with 500 holes in a spinning pack consisting of a combination of screen , filter, flow partitioning and supporting plates.

After spinning 500 filaments from the spinning cap through a 12 mm air gap, the temperature of the bath solution is adjusted to 20 ° C in a 20% phosphoric acid aqueous solution equipped with a quenching tube with a diameter of 5 mm. Yarn is generated by coagulating while coagulating. Advance the yarn forward with a pair of feed rolls that feed the yarn 200 meters per minute.

Hydrolysis and cleaning The yarn is first rinsed with water in a cleaning container and then rinsed on a roll. The yarn is then brought into contact with a cylindrical pin to remove most of the liquid on the surface. The yarn is then fed to a drying roll operating at a surface temperature of 105 ° C. The time that the yarn is in contact with the surface of the roll is set to 4.2 seconds.

The yarn is then sent to an electrically heated roll operating at a surface temperature of 200 ° C. to hydrolyze the PPA remaining on the filament. In addition to allowing the total time to move on the roll to be 14 seconds, the yarn should be in contact with the surface of the roll for 7 seconds.

The yarn is then sent to a cleaning roll and washed to remove residual acid. The yarn is passed through 8 pairs of advancing-wrap wash rolls. The number of turns for each roll pair is 10, the residence time is 7.5 seconds, and the temperature of the cleaning solution is adjusted to 70 ° C.

A step of cleaning the yarn with countercurrent water is performed on the first four sets of cleaning rolls. By extracting phosphoric acid from the yarn, the amount of phosphoric acid in the washing water increases from the fourth set of rolls toward the first set of rolls.

The yarn is washed with 2% sodium hydroxide in water on a fifth set of washing rolls and then the yarn is washed with water on a sixth set of washing rolls. During this operation, some caustic is carried from the fifth set of cleaning rolls to the sixth set of rolls.

The yarn is washed with 2% acetic acid in water on the 7th set of washing rolls and then the yarn is washed with water on the 8th set of washing rolls. During this operation, some acetic acid is carried from the 7th set of cleaning rolls to the 8th set of rolls.

Dry The washed yarn is transferred through a pair of rolls for the purpose of isolating the wash from drying. After removing most of the surface cleaning solution from the yarn by passing it between the cylindrical pins in contact, it is transferred onto a pair of steam heating and drying rolls with a surface temperature of 150 ° C. .. The contact time on the drying roll is set to 30 seconds. The textile finish is then applied to the yarn and then wound onto the bobbin.

In this example, any heat treatment of the yarn generated in Example 11 will be described. The method of Example 11 is repeated except that the dried yarn is coated with a volatile chargeable finish instead of a textile finish and the yarn is immediately sent to a heating roll instead of being wound onto a bobbin.

Heat treatment The dried yarn is sent to three pairs of electrically heated rolls to raise the temperature of the yarn to 400 ° C. Next, N the yarn₂The temperature of the yarn is raised to 500 ° C by transferring it into a tube oven under the blanket. The yarn is N₂N at room temperature before leaving the atmosphere₂After cooling in an atmosphere for 2 seconds, apply the finishing agent. The yarn is then transferred through a set of rolls to establish a tension suitable for winding, and then the yarn is wound onto a tube by a tension control spindle driven winder.

This is a clean, dried 4CV Model DIT Mixer [available from Design Integrated Technology, Inc (100E. Franklin St., Warrenton, VA 20186 (888) 567-8213)], constantly purged with nitrogen gas. In the following together: a) P₂O₅585.71 grams of polyphosphoric acid (PPA) with a concentration equivalent to 84.84%, b) P₂O₅168.90 grams, c) 3 grams of tin powder [325 mesh, available from VWR scientific; make the amount of this tin powder about 1.2% by weight based on the amount of TD complex], and d) 245.44 grams of TD complex [a 1: 1 complex of tetraaminopyridine (TAP) and dihydroxyterephthalic acid, ie 101.28 g of TAP and 144.21 g of DHTA].

The 4CV Model is a jacketed bipyramid reaction vessel that heats the jacket by circulating hot oil, which is a double helix that intersects each other over the entire conical envelope of the bowl. A conical blade was used, giving a unique mixing principle. After starting the blades of the mixer and setting it to 80 rpm, the reaction mixture was evacuated in a manner such that foaming of the mixture during the reaction was suppressed. The temperature of the reaction mixture is measured with a thermocouple throughout. The temperature was raised to 100 ° C and held for 1 hour. The temperature was then raised to 135 ° C and held for 2 hours. Next, the mixer is nitrogen-free. Flash wash with gas. Next, P to the mixing device₂O₅Add 55.2 grams of a mixture of 49.73 grams of PPA and 5.49 g of water, which corresponds to a concentration of 84.84%. The solution is stirred for 15 minutes. The temperature is then raised to 180 ° C. and held for 2 hours, after which a vacuum is applied to the mixer for the last 30 minutes of polymerization. Next, after purging the mixing device with nitrogen, the polymer solution was discharged into a glass container. This polymer was taken out from the mixing device in the form of 18.29% of the polymer in PPA. A sample of the polymer solution was diluted with methanesulfonic acid to a concentration of 0.05%. n_inh=23.9。

A detailed explanation as well as the summary described above will be further understood by reading in connection with the attached figure. For purposes of exemplifying the invention, typical embodiments of the invention are shown in this figure, however, the invention is not limited to the specific methods, compositions and devices disclosed therein.<u style="single">Next, a preferred embodiment of the present invention will be shown.</u><u style="single">1. A method for continuously producing polyarene azole multifilament yarn.</u><u style="single">a) A filament is formed by extruding a solution containing a polyarene azole polymer and polyphosphoric acid through a number of orifices.</u><u style="single">b) Generate multifilament yarn from the filament</u><u style="single">c) By heating the yarn to a temperature of about 120 ° C or higher within about 2 minutes, at least some of the polyphosphoric acid contained in the yarn is hydrolyzed.</u><u style="single">d) Rinse at least some of the polyphosphoric acid hydrolyzate from the yarn and</u><u style="single">e) Dry the washed yarn and</u><u style="single">f) In some cases, heat the yarn above about 300 ° C and</u><u style="single">g) Collect the yarns at a speed of at least about 50 meters per minute,</u><u style="single">A method that includes things.</u><u style="single">2. The method according to 1 above, which additionally comprises subjecting the yarn before being hydrolyzed to undergo adjustment.</u><u style="single">3. The method according to 1 above, wherein the extruded filament is passed through an air gap and then into a coagulation bath.</u><u style="single">4. The method according to 1 above, wherein the solution is a liquid crystal solution.</u><u style="single">5. The polyarene azole polymer is a polymer generated from an azole-producing monomer, in which the monomer is 2,5-dimercapto-p-phenylenediamine, terephthalic acid, bis- (4). -Benzoic acid), oxy-bis- (4-benzoic acid), 2,5-dihydroxyterephthalic acid, isophthalic acid, 2,5-pyridodicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,6-quinolindicarboxylic acid Acid, 2,6-bis (4-carboxyphenyl) pyridobis imidazole, 2,3,5,6-tetraaminopyridine, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, 2,5-diamino- The method according to 1 above, which is 4,6-dithiobenzene or any combination thereof.</u><u style="single">6. The method according to 5 above, wherein the azole-forming monomer is 2,3,5,6-tetraaminopyridine and 2,5-dihydroxyterephthalic acid.</u><u style="single">7. The method according to 2 above, wherein the adjustment comprises removing surface liquid from the yarn.</u><u style="single">8. The method according to 7 above, in which the yarn is rinsed with an aqueous solution before removing the liquid on the surface.</u><u style="single">9. The method according to 1 above, wherein at least some of the polyphosphoric acid contained in the yarn is hydrolyzed by heating the yarn to a temperature of about 150 ° C. or higher.</u><u style="single">10. The method according to 9 above, wherein at least some of the polyphosphoric acid contained in the yarn is hydrolyzed by heating the yarn to a temperature of about 180 ° C. or higher.</u><u style="single">11. The method according to 10 above, wherein at least some of the polyphosphoric acid contained in the yarn is hydrolyzed by heating the yarn to a temperature of about 200 ° C. or higher.</u><u style="single">12. The method according to 1 above, wherein the washing comprises contacting the yarn with an aqueous base solution.</u><u style="single">13. The method according to 1 above, wherein the washing comprises contacting the yarn with an aqueous acid solution followed by contact with an acid water soluble solution.</u><u style="single">14. The method according to 1 above, wherein the washing comprises bringing the yarn into contact with water.</u><u style="single">15. The method according to 1 above, wherein the yarn is dried to a water content of less than about 20 weight percent.</u><u style="single">16. The method according to 1 above, in which the yarn is heated to a temperature of about 400 ° C. or higher in step f).</u><u style="single">17. The method of 1 above, where the yarn is collected at a speed of at least about 100 meters per minute.</u><u style="single">18. The method of 1 above, where the yarns are collected at a speed of at least about 250 meters per minute.</u><u style="single">19. The method of 1 above, where the yarns are collected at a speed of at least about 500 meters per minute.</u><u style="single">20. The method of 1 above, where the yarns are collected at a speed of at least about 800 meters per minute.</u>

<figref num="1">FIG. 1 is a schematic diagram of a method for producing a polyarene azole fiber.</figref><figref num="2">FIG. 2 is a graph showing the intrinsic viscosity of the polyarene azole polymer solution according to the specific aspect of the present invention shown in Table 4 in comparison with the tin content.</figref>